Polychloro-7, 8-disubstituted-2, 5-diimino glycoluril for use as an antivesicant



POLYCHLORO 7,8 DISUBUSTITUTED 2,5 DI- IMINO GLYCOLURIL FOR" use AS AN ANTI- VESICANT I John C. Speck, Jr., Bloomington, Ind.

No Drawing. Application March 13, 1944 Serial No. 526,309

Claims. (Cl. 117-121) (Granted under Title 35, US. Code (1952), sec. 266) such as mustard gas or organic chloroarsines, it is neces- I sary to neutralize the vesicant before the area can be safely entered. Also it is necessary to provide workers in contaminated areas with suitable protective clothing. Clothing which seals thebody'from contact with the air cannot be wom'ror long periods'in'hot weather, be- I cause the only way thebody temperature may be maintained is by evaporation of perspiration. Therefore, it is necessary to provide porous clothing which is impregnated with a substance which will neutralize substantially all vesicant vapor coming in contact with the clothing.)

the body In this way air is permitted to circulate around without harm.v Substances'which are useful for decontamination of afiected areas must of course show instantaneous reactivity with. the vesicant vapors. If they are to be used for. impregnation of clothing they must additionally be harmless to the skin and stable to oxygen, water and sunlight. They must also cause little or no increase in flammability or deterioration of the cloth, they must withstand removal or decomposition by laundering and they must be thermally stable at all temperatures likely to be encountered in use. Other desirable properties include stability in solution or in the presence of a solvent so that appreciable decomposition does not occur during impregnation, easy preparation from readily available raw materials with simple apparatus, and high efliciency and protective time so. that great quantities of the substance and frequent replenishment are not required.

It is well known that compounds containing reactive chlorine are useful neutralizers or anti-vesicants for mustard gas and other vesicant vapors, and organic com- .poundscontaining a chloroamide group are generally preferred, An eflicient class of compounds known heretofore are the tetrachloro disubstituted"glycolurils,such as 1,3,4,6-tetrachloro-7,S-dimethyl glycoluril which is used extensively. These chlorinated glycolurils, however, are more or less irritating-to the skin when in contact therewith -over prolonged periods of time, although they are less so than other generally known chloroamide compounds. Also, the chlorinated glycolurils are relatively hard on textile fibers, and clothing impregnated therewith will not Withstand for, long the rough treatinvent given army clothing under fighting conditions.

This invention provides a new class of anti-vesicants which are characterized by their high efliciency and long protective times, and in this respect are similar to the above-mentioned chlorinated glycolurils to which they are chemically related. Unlike the chlorinated glycolurils, however, the new compounds are less irritating tofthe skin and do not adversely affect clothing to the same extent. The invention includes these new compounds per se and anti-vesicants containing them. I Also included are protective materials containing the compounds, particularly ointments, dusting powders and impregnated clothing.

The anti-vesicants of this invention are of the class of chloroamides may be described as chlorinated 7,8-disubstituted-2,5-diimino glycolurils, having the following structural formula:

wherein R and R are aryl, or aralkyl radicals and X and X are hydrogen or chlorine. The preferred compounds are those in which X and X are hydrogen (i.e. the 1,3,4,6 tetrachloro-7,8-disubstituted-2,5-diimino gly colurils) and of these the 7,8-diphenyl compound'is particularly desirable. This compound has the structural formula EXAMPLE Condensation A solution of guanidine (1 mole, 59 grams) inl liter of 95% ethanol is prepared by heating one mole of sodium ethoxide (sodium hydroxide can be used) with the calculated amount of guanidine nitrate (1 mole), then cooling and filtering 01f the sodium nitrate formed..-

The filtrate containing the guanidine is reacted with a solution of 0.5 mole of benzil in 3 liters of 95% ethanol by heating up to five hours or letting stand over night. In place of the free guanidine solution, a basic salt thereof, such as guanidine carbonate, can be used directly in the condensation reaction.

Separation of base I-fguanidine carbonate is not used-, the alcoholic liquor is filtered and the filtrate saturated with carbon dioxide, with the formation of a copious precipitate. If guanidine carbonate is used, the liquor is filtered directly, as the base precipitates during reaction. The precipitate is purified by washing with cold ethanol and recrystallizing from a mixture of half alcohol and half water. -1-

Chlorination ass 5,305

about 1.25 moles of a buffer salt, such as sodium bicarbonate or acetate, and about 75 ml. of a 1% solution of dioctyl sodium sulfosuccinate or similar wetting agent. Chlorine gas is passed into the water with vigorous stirring until the calculated amount (about 80 grams), as determined by periodic weighing of the chlorine cylinder; has been absorbed. The material is filtered, washed with water and dried.

The above method of chlorination yielded essentially 1,3,4,6-tetrachloro-7,8-diphenyl-2,5-diimino glycoluril as only enough chlorine was added to give this compound. Where it is desirable to obtain the hexachloro derivative, the addition of chlorine is continued until the calculated mount for the addition of six chlorine atoms is absorbed. However, for use as an antivesicant the advantages of the higher active chlorine content of the hexachloro compound is offset to a large extent by the fact that the chlorine attached to the imino groups is less stable than the other chlorine and renders the compound somewhat more irritating to the skin and deleterious to fabrics.

Thermal stability tests and tests of hydrolytic stability and stability in chlorinated hydrocarbons have shown that the chlorinated diimino glycoluril derivatives of this invention are equally as stable as the corresponding chlorinated glycolurils and much more stable under many conditions. As already indicated, the diimino compounds are less irritating to the skin, less injurious to fabrics and provide equally effective protection against the action of vesicant vapors, particularly of the mustard type.

Clothing may be impregnated with these compounds or mixtures thereof, with or without other materials, in any of the standard ways employed for other chloroarnide anti-vesicant compounds.

The incorporation of the compounds of this invention in dusting powders is satisfactory because the powders do not plug the pores and provide good protection. For this purpose, talc is a suitable inert material with some substance added to keep the powder free flowing (e.g. various phosphate salts).

For use in ointments, the compounds may be incorporated in any standard inert ointment composition such as those using triacetin as a base.

The term anti-vesicant, as used herein, refers to substances or compositions capable of rendering harmless or neutralizing vesicant materials, particularly mustard gas.

The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

I claim:

1. A polychloro-7,8-disubstituted-2,5-diimino glycoluril of the general formula:

wherein R and R are selected from the group consisting of aryl and aralkyl radicals and X and X are selected from the group consisting of hydrogen and chlorine.

2. As a new compound, a 1,3,4,6-tetrachloro-7,8-diaryl-2,5-diimino glycoluril.

3. As a new compound, 1,3,4,6 tetrachloro 7,8 di phenyl-2,5-diimino glycoluril.

4. An article of clothing protective against vesicants which comprises a porous material impregnated with a substance comprising essentially a 1,3,4,6-tetrachloro-7,8- diaryl-2,5-diimino glycoluril.

5. An article of clothing protective against vesicants which comprises a porous material impregnated with a 1 substance comprising essentially a chemical compound having the structural formula 8. A dusting powder suitable for protection against vesicants which comprises an inert powder admixed with a 1,3,4,6-tetrachloro-7,8-diaryl-2,S-diimino glycoluril.

9. A dusting powder suitable for protection against vesicants which comprises an inert powder admixed with a chemical compound having the structural formula 10. A vehicle with which is incorporated as an essential active ingredient a polychloro-7,8-disubstituted-2,5- diimino glycoluril of the general formula Cl R1 01 wherein R and R, are selected from the group consisting of aryl and aralkyl radicals and X and X are selected from the group consisting of hydrogen and chlorine.

References Cited in the file of this patent UNITED STATES PATENTS 2,005,538 Engelmann June 18, 1938 2,155,914 Van der Lee Apr. 25, 1939 2,351,924 Carnaugh June 20, 1944 

1. A POLYCHLORO-7,8-DISUBSTITUTED-2,5-DIIMINO GLYCOLURIL OF THE GERERAL FORMULA:
 4. AN ARTICLE OF CLOTHING PROTECTIVE AGAINST VESICANTS WHICH COMPRISES A POROUS MATERIAL IMPREGNATED WITH A SUBSTANCE COMPRISING ESSENTIALLY A 1,3,4,6-TETRACHLORO-7,8DIARYL-2,5-DIIMINO GLYCOLURIL. 